Impregnation process for a fibrous substrate, a liquid (meth) acrylic syrup for the impregnation process, its method of polymerization and structured article obtained thereof

ABSTRACT

The present invention relates to an impregnation process for a fibrous substrate, a liquid composition for implementing this process and the obtained impregnated fibrous substrate. The impregnated fibrous substrate is suitable for manufacturing mechanical or structured parts or articles. In particular the present invention deals with an industrial process for impregnating a fibrous substrate or long fibers with a viscous liquid composition containing mainly methacrylic or acrylic components. This viscous composition is called hereafter liquid (meth) acrylic syrup. The invention concerns also a fibrous substrate pre-impregnated with said syrup which is useful for manufacturing mechanical or structured parts or articles. More particular the impregnation of fibrous substrate with the (meth) acrylic syrup is achieved in a closed mould. The present invention concerns also manufacturing process for manufacturing mechanical or structured parts or articles and three-dimensional mechanical or structured parts obtained by this process.

REFERENCE TO PRIOR APPLICATIONS

This application is a division of copending U.S. application Ser. No.14/414,732, filed Jan. 14, 2015, which is a national stage applicationof PCT/EP2013/065218, filed Jul. 18, 2013, which claims benefit, underU.S.C. § 119(a) of French National Application Number FR12.56929, filedJul. 18, 2012. Each of the foregoing applications is incorporated hereinby reference in its entirety for all purposes.

FIELD OF THE INVENTION

The present invention relates to an impregnation process for a fibroussubstrate, a liquid composition for implementing this process and theobtained impregnated fibrous substrate. The impregnated fibroussubstrate is suitable for manufacturing mechanical or structured partsor articles.

In particular the present invention deals with an industrial process forimpregnating a fibrous substrate or long fibers with a viscous liquidcomposition containing mainly methacrylic or acrylic components. Thisviscous composition is called hereafter liquid (meth) acrylic syrup. Theinvention concerns also a fibrous substrate pre-impregnated with saidsyrup which is useful for manufacturing mechanical or structured partsor articles.

More particular the impregnation of fibrous substrate with the (meth)acrylic syrup is achieved in a closed mould.

The present invention concerns also manufacturing process formanufacturing mechanical or structured parts or articles andthree-dimensional mechanical or structured parts obtained by thisprocess.

TECHNICAL PROBLEM

Mechanical or structured parts or articles that have to absorb highstresses during their use are widely manufactured from compositematerials. A composite material is a macroscopic combination of two oremore non miscible materials. The composite material constitutes at leastof a matrix material that forms a continuous phase for the cohesion ofthe structure and a reinforcing material with various architectures forthe mechanical properties.

The aim in using composite materials is to achieve a performance fromthe composite material that is not available from its separateconstituents if used alone. Consequently composite materials are widelyused in several industrial sectors as for example building, automotive,aerospace, transport, leisure, electronics, and sport notably due totheir better mechanical performance (higher tensile strength, highertensile modulus, higher fracture toughness) in comparison withhomogenous materials and their low density.

The most important class in view of volume in commercial industrialscale, are composites with organic matrices, where the matrix materialis a generally polymer. The principal matrix or continuous phase of apolymeric composite material is either a thermoplastic polymer or athermosetting polymer.

Thermosetting polymers consist of crosslinked three dimensionalstructures. The crosslinking is obtained by curing reactive groupsinside the so called prepolymer. Curing for example can be obtained byheating the polymer chains in order to crosslink and harden the materialpermanently.

In order to prepare the polymeric composite material the prepolymer ismixed with the other component such as glass beads or fibres or theother component which is wetted or impregnated and cured afterwards.Example for prepolymers or matrix material for thermoset polymers areunsatured polyesters, vinylesters, epoxy or phenolic ones.

A major disadvantage of a thermoset polymer matrix is its rigidity. Thematrix cannot be easily shaped in other forms. Once the polymer has beencured the form is fixed. This makes also difficult the recycling of thethermoset composite material and manufactured mechanical or structuredparts or articles comprising said thermoset composite material, whichare burned in a cement plant or thrown into a waste dump.

Thermoplastic polymers consist of linear or branched polymers, which arenot crosslinked. The thermoplastic polymers are heated in order to mixthe constituents necessary for producing the composite material and tobe cooled for setting. The limit in using thermoplastic polymers for thefabrication of composite materials is their high viscosity in the moltenstate in order to homogenously impregnating for example a fibroussubstrate. The wetting or correct impregnation of the fibers by thethermoplastic polymer can only be achieved, if the thermoplastic resinis sufficiently fluid. In order to have a low viscosity or sufficientfluidity of the thermoplastic polymer the chain length or molecular massshall be reduced. However a too low molecular weight has a negativeimpact on the performance of the composite material and on themechanical or structured parts especially their mechanical properties asthe deformation modulus.

Another way to reduce the viscosity in an important way of thethermoplastic polymer is to increase the temperature. Consequently thecontinuous working temperature is relatively high, above 200° C.,increasing the economics costs of the composite material and mechanicalor structured parts due to implication of high energy costs.Additionally thermoplastic polymers tend to degrade if the temperatureis too high, which is especially true for semicrystalline thermoplasticpolymers that have high melting points as for example polyamides such asPA6.6, polyethersulfon (PES), polyetherimid (PEI), polyetheretherketon(PEEK) or polyphenylene sulfide (PPS). This thermoinduced degradationyields to a decreasing molecular weight of the polymer matrix on thefibrous substrate important for the cohesion of the composite materialand the mechanical or structured parts.

Another way for impregnating the fibrous substrate is to dissolve thethermoplastic polymer in an organic solvent. However this methodrequires a lot of solvent that has to be evaporated. There areenvironmental issues in using large quantities of solvent in term ofenergy and pollution.

These are the limits or disadvantages for the preparation ofthermoplastic composite materials especially with fibrousreinforcements, the impregnation process for a fibrous substrate and themanufactured mechanical or structured parts or articles comprising saidthermoplastic composite material.

The objective of the present invention is to solve the disadvantagesmentioned above.

One objective of the present invention is to have a structural partcomprising a thermoplastic composite material with satisfying mechanicalproperties such as high stiffness and a young modulus of at least 15GPa.

Another objective of the present invention is to have a structural partcomprising a thermoplastic composite material with a satisfying UVresistance.

The further objective of the present invention is to have a structuralpart comprising a thermoplastic composite material that can betransformed and shaped into form due to a certain flexibility.

Still another objective of the present invention is to wet completely,correctly and in a homogenous way the fibrous substrate duringimpregnation. Any defects of fiber wetting for example by bubbles andvoids decrease the mechanical performance of the structural part.

Another objective of the present invention is the recycling of thestructural part including the composite material or structural partsthat do not meet quality standards or worn-out structural parts. Underrecycling is understood to recover at least a part of the used rawmaterials. This means grinding and reusing the thermoplastic polymer.This means also for example that the monomer from the thermoplasticmatrix of the composite material can be recovered.

Another objective of the present invention is to provide a process whichcan be carried out at low cost and is capable of large-scalemanufacturing, to produce the structural parts comprising thethermoplastic composite material of the invention. In addition, theprocess should be easy and simple to carry out using commerciallyavailable components. Also the manufacturing of parts should bereproducible and fast meaning short cycle times.

BACKGROUND OF THE INVENTION

The document FR 1374046 describes a process of polymerization of acrylicmonomers especially methacrylic monomers from monomer-polymer syrupsusing a metal catalyst based on tin. Glass fibres are impregnated with amethanol solution of the tin catalyst. Afterwards the fibres areimpregnated with a monomer-polymer syrup and then the composition ispolymerized. The process uses a metal catalyst and the impregnation andpolymerization are not made in a closed mold or the same closed mold.

The document JP9085841 describes the preparation of a fabric basecomposite thermoplastic plastic member. A thermoplastic polymer isdissolved in a volatile solvent and mixed with the fabric base material.The solvent is evaporated and the prepreg is cut into shapes, then it iscoated again with the solution of thermoplastic polymer in a solvent andcured by evaporation of the solvent. In the example apolymethylmethacrylate as thermoplastic polymer is dissolved at 15 wt %in a solvent mixture consisting of methanol, xylene, tetrahydrofyran inorder to impregnate the fibrous material. This preparation method uses alot of solvent that evaporates.

The document EP0796873 discloses a (meth)acrylic syrup, a process forfor preparing the syrup and a process for preparing molding materialcontaining the (meth)acrylic syrup. The main objective is having a syrupwith excellent storage stability. The molding material might include areinforcing material in form of fibres. However the mixing of thereinforcing material and the syrup is not made by impregnation processin a closed mold.

In the prior no impregnation process for impregnating a fibroussubstrate is described where the fibrous substrate and the liquid (meth)acrylic syrup are brought into contact before the polymerizationaccording to the present invention.

In the prior no manufacturing process for manufacturing mechanical orstructured parts or articles is described including the impregnationprocess for impregnating a fibrous substrate with a liquid (meth)acrylic syrup and polymerization according to the present invention.

BRIEF DESCRIPTION OF THE INVENTION

Surprisingly it has been found that an impregnation process forimpregnating a fibrous substrate, wherein said fibrous substrate is madeof long fibres and said process comprises a step of impregnating saidfibrous substrate with a liquid (meth) acrylic syrup comprising:

-   -   a) a (meth)acrylic polymer,    -   b) a (meth)acrylic monomer,    -   c) at least one initiator or initiating system for starting the        polymerization of the (meth) acrylic monomer,        said liquid (meth)acrylic syrup has a dynamic viscosity of a        value in the range from 10 mPa*s to 10000 mPa*s, preferably from        50 mPa*s to 5000 mPa*s and advantageously from 100 mPa*s to 1000        mPa*s yields to a complete and correct impregnation of the        fibrous substrate.

Surprisingly it has also been discovered that an impregnation liquid(meth) acrylic syrup for implementing the impregnation process for afibrous substrate, said liquid (meth) acrylic syrup comprises:

-   -   a) a (meth)acrylic polymer,    -   b) a (meth)acrylic monomer,    -   c) at least one initiator or initiating system for starting the        polymerization of the (meth) acrylic monomer,        said liquid (meth)acrylic syrup has a dynamic viscosity of a        value in the range from 10 mPa*s to 10000 mPa*s, preferably from        50 mPa*s to 5000 mPa*s and advantageously from 100 mPa*s to 1000        mPa*s yields to a complete and correct impregnation of the        fibrous substrate.

Surprisingly it has also been discovered that a manufacturing processfor manufacturing mechanical or structured parts or articles comprisingfollowing steps:

a) impregnating a fibrous substrate with a liquid (meth) acrylic syrup,

b) polymerising the liquid (meth) acrylic syrup impregnating saidfibrous substrate yields to manufactured mechanical or structured partsor articles having satisfying mechanical properties by possessing a highstiffness and a young modulus of at least 15 GPa.

Additionally it has also been discovered that a three-dimensionalmechanical or structured parts obtained by the manufacturing processpossessing a high stiffness and a young modulus of at least 15 GPa, hasnearly no defects as voids between the fibrous substrate and the(meth)acrylic polymer.

DETAILED DESCRIPTION OF THE INVENTION

According to a first aspect, the present invention relates to animpregnation process for impregnating a fibrous substrate, wherein saidfibrous substrate is made of long fibres and said process comprises astep of impregnating said fibrous substrate with a liquid (meth) acrylicsyrup comprising:

-   -   a) a (meth)acrylic polymer,    -   b) a (meth)acrylic monomer,    -   c) at least one initiator or initiating system fir starting the        polymerization of e (meth) acrylic monomer,        said liquid (meth)acrylic syrup has a dynamic viscosity of a        value in the range from 10 mPa*s to 10000 mPa*s, preferably from        50 mPa*s to 5000 mPa*s and advantageously from 100 mPa*s to 1000        mPa*s.

According to another aspect the impregnation process of the fibroussubstrate of the present invention is made in a closed mold.

According to still another aspect the impregnation process of thefibrous substrate of the present invention is made with a liquid (meth)acrylic syrup that comprises a (meth)acrylic polymer which is a homo- orcopolymer of methyl methacrylate (MMA) or a mixture thereof.

By the term “fibrous substrate” as used are denoted fabrics, felts ornonwovens that may be in the form of strips, laps, braids, locks orpieces.

By the term “(meth)acrylic” as used is denoted all kind of acrylic andmethacrylic monomers.

By the term “PMMA” as used are denoted homo- and copolymers ofmethylmethacrylate (MMA), for the copolymer of MMA the weight ratio ofMMA inside the PMMA is at least 70 wt %.

By the term “monomer” as used is denoted is a molecule which can undergo polymerization.

By the term “polymerization” as used is denoted the process ofconverting a monomer or a mixture of monomers into a polymer.

By the term “thermoplastic polymer” as used is denoted a polymer thatturns to a liquid or becomes more liquid or less viscous when heated andthat can take on new shapes by the application of heat and pressure.

By the term “thermosetting polymer” as used is denoted a prepolymer in asoft, solid or viscous state that changes irreversibly into aninfusible, insoluble polymer network by curing.

By the term “polymer composite” as used is denoted a multicomponentmaterial comprising multiple different phase domains in which at leastone type of phase domain is a continuous phase and in which at least onecomponent is a polymer.

By the term “initiator” as used is denoted a chemical species that'sreacts with a monomer to form an intermediate compound capable oflinking successively with a large number of other monomers into apolymeric compound.

With regard to structured part or article this concerns a panel, a coveror a hull made of composite material or parts for aircrafts, for boats(hull and deck), rail cars (hatch, partition, body), and automotiveparts (car body, hood, door.)

With regard to the (metha)acrylic polymer, one could mention poly alkylmethacrylates or poly alkyl acrylates. In a preferred embodiment the(meth)acrylic polymer is poly methyl methacrylate (PMMA).

The term “PMMA” denotes a methyl methacrylate (MMA) homopolymer or acopolymer or mixtures thereof.

In one embodiment the homo- or copolymer of methyl methacrylate (MMA)comprises at least 70%, preferably at least 80%, advantageously at least90% and more advantageously at least 95% by weight of methylmethacrylate.

In another embodiment the PMMA is a mixture of at least one homopolymerand at least one copolymer of MMA, or a mixture of at least twohomopolymers or two copolymers of MMA with a different average molecularweight or a mixture of at least two copolymers of MMA with a differentmonomer composition.

The copolymer of methyl methacrylate (MMA) comprises from 70% to 99.7%by weight of methyl methacrylate and from 0.3 to 30% by weight of atleast one monomer having at least one ethylenic unsaturation that cancopolymerize with methyl methacrylate.

These monomers are well known and mention may be made, in particular ofacrylic and methacrylic acids and alkyl(meth)acrylates in which thealkyl group has from 1 to 12 carbon atoms. As examples, mention may bemade of methyl acrylate and ethyl, butyl or 2-ethylhexyl (meth)acrylate.Preferably the comonomer is an alkyl acrylate in which the alkyl grouphas from 1 to 4 carbon atoms.

In a preferred embodiment the copolymer of methyl methacrylate (MMA)comprises from 70% to 99.7%, preferably from 80% to 99.7% advantageouslyfrom 90% to 99.7% and more advantageously from 90% to 99.5% by weight ofmethyl methacrylate and from 0.3% to 30%, preferably from 0.3% to 20%advantageously from 0.3% to 10% and more advantageously from 0.5% to 10%by weight of at least one monomer having at least one ethylenicunsaturation that can copolymerize with methyl methacrylate. Preferablythe comonomer is chosen from methyl acrylate or ethyl acrylate ormixtures thereof.

The weight average molecular weight of the (meth)acrylic polymer shouldbe high, meaning larger than 50 000 g/mol, preferably larger than 100000 g/mol.

The weight average molecular weight can be measured by size exclusionchromatography (SEC).

With regard to the (meth)acrylic monomer, the monomer is chosen fromacrylic acid, methacrylic acid, alkyl acrylic monomers, alkylmethacrylic monomers and mixtures thereof.

Preferably the monomer is chosen from acrylic acid, methacrylic acid ,alkyl acrylic monomers, alkyl methacrylic monomers and mixtures thereof,the alkyl group having from 1 to 22 carbons, either linear, branched orcyclic; preferably the alkyl group having from 1 to 12 carbons, eitherlinear, branched or cyclic.

Advantageously the meth)acrylic monomer is chosen from methylmethacrylate, ethyl methacrylate, methyl acrylate, ethyl acrylate,methacrylic acid, acrylic acid, n-butyl acrylate, iso-butyl acrylate,n-butyl methacrylate, iso-butyl methacrylate, cyclohexyl acrylate,cyclohexyl methacrylate, isobornyl acrylate, isobornyl methacrylate andmixtures thereof.

More advantageously the monomer is chosen (meth)acryiic monomer ischosen from methyl methacrylate, isobornyl acrylate or acrylic acid andmixtures thereof.

In a preferred embodiment at least 50 wt %, preferably at least 60 wt %of the monomer is methyl methacrylate.

In a more preferred embodiment at least 50 wt %, preferably at least 60wt %, more 90 wt % of the monomer is a mixture of methyl methacrylatewith isobornyl acrylate and/or acrylic acid.

With regard to the fibrous substrate, one can mention fabrics, felts ornonwovens that may be in the form of strips, laps, braids, locks orpieces. The fibrous material can have different forms and dimensionseither one dimensional, two dimensional or three dimensional. A fibroussubstrate comprises an assembly of one or more fibres. When the fibresare continuous, their assembly forms fabrics.

The one dimensional form is linear long fibres. The fibers may bediscontinuous or continuous, The fibers may be arranged randomly or as acontinuous filament parallel to each other. A fiber is defined by itsaspect ratio, which is the ratio between length and diameter of thefiber. The fibers used in the present invention are long fibers orcontinuous fibers. The fibers have an aspect ratio of at least 1000,preferably at least 1500, more preferably at least 2000, advantageouslyat least 3000 and most advantageously at least 5000.

The two dimensional form are fibrous mats or non woven reinforcements orwoven roving or bundles of fibers, which can also be braded.

The three dimensional form are for example stacked or folded fibrousmats or non woven reinforcements or bundles of fibers or mixturesthereof, an assembly of the two dimensional form in the third dimension.

The origins of the fibrous material can be a natural or a synthetic one.As natural material one can mention vegetable fibers, wood fibers,animal fibers or mineral fibers.

Natural fibers are for example sisal, jute, hemp, flax, cotton, coconutfibers, and banana. fibers. Animal fibers are for example wool or hair.

As synthetic material one can mention polymeric fibers chosen fromfibers of thermosetting polymers, from thermoplastic polymers or theirmixtures.

The polymeric fibers can be made of polyamide (aliphatic or aromatic),polyester, polyvinylacohol, polyolefins, polyurethanes,polyvinylchloride, polyethylene, unsatured polyesters, epoxy resins andvinylesters.

The mineral fibers can also be chosen from glass fibers especially oftype E, R or S2, carbon fibers, boron fibers or silica fibers.

The fibrous substrate of the present invention is chosen from vegetablefibers, wood fibers, animal fibers, mineral fibers, synthetic polymericfibers, glass fibers, carbon fibers or mixtures thereof.

Preferably the fibrous substrate is chosen from mineral fibers.

With regard to the initiator or initiating system for starting thepolymerization of the (meth) acrylic monomer, one could mentioninitiators or initiating systems that are activated by heat.

The heat activated initiator is preferably a radical initiator.

With regard to the radical initiator, they can be chosen from diacylperoxides, peroxy esters, dialkyl peroxides, peroxyacetals or azocompounds.

The initiator or initiating system for starting the polymerization ofthe (meth) acrylic monomer is chosen from isopropyl carbonate, benzoylperoxide, lauroyl peroxide, caproyl peroxide, dicumyl peroxide,tert-butyl perbenzoate, tert-butyl per(2-ethylhexanoate), cumylhydroperoxide, 1,1-di(tert-butylperoxy)-3,3,5-trimethylcyclohexane,tert-butyl peroxyisobutyrate, tert-butyl peracetate, tert-butylperpivalate, amyl peripivalate, tert-butyl peroctoate,azobisisobutyronitrile (AIBN), azobisisobutyramide,2,2′-azobis(2,4-dimethylvaleronitrile) or 4,4′-azobis(4-cyanopentanoic).It would not be departing from the scope of the invention to use amixture of radical initiators chosen from the above list.

Preferably the initiator or initiating system for starting thepolymerization of the (meth) acrylic monomer is chosen from peroxideshaving 2 to 20 carbon atoms

The content of radical initiator with respect to the (meth)acrylicmonomer of the a liquid (meth) acrylic syrup is from 100 to 50000 ppm byweight (50000 ppm=5 wt %), preferably between 200 and 40000 ppm byweight and advantageously between 300 and 30000 ppm.

The (meth)acrylic monomer is typically one or more monomers as definedabove with, optionally, a suitable inhibitor such as hydroquinone (HQ),methyl hydroquinone (MEHQ), 2,6-di-tertiary-butyl-4-methoxyphenol(Topanol O) and 2,4-dimethyl-6-tertiary-butyl phenol (Topanol A).

The inhibitor is present to prevent the monomer from spontaneouslypolymerising.

The liquid (meth) acrylic syrup comprises optionally also an activatorfor the polymerization.

Polymerisation activator or accelerator is chosen from tertiary aminessuch as N,N-dimethyl-p-toluidine (DMPT), N,N-dihydroxyethyl-p-toluidine(DHEPT), organic-soluble transition metal catalysts or mixtures thereof.

Advantageously the liquid (meth) acrylic syrup contains no metal basedcatalysts. No metal comprising additives as activators for catalyticallyaccelerate the polymerization reaction are added to liquid (meth)acrylic syrup the liquid (meth) acrylic syrup according to theinvention. These concerns especially tin based compounds as tinchloride.

The content of the activator with respect to the to the (meth)acrylicmonomer of the liquid (meth) acrylic syrup is from 100 ppm to 10000 ppm(by weight), preferably from 200 ppm to 7000 ppm by weight andadvantageously from 300 ppm to 4000 ppm.

The presence of activators or accelerators depends upon the finalapplication. Where “cold-cure” is necessary or wished, an accelerator isusually necessary. Cold cure means that the polymerization takes placeat ambient temperature, meaning less than 50° C. or preferably less than40° C.

However, for industrial applications the use of heat in “heat-cure”systems is also possible.

Another ingredient in the liquid resin can also be a chain-limitingagent in order to control the molecular weight, for example γ-terpineneor terpinolene, at contents of between 0 and 500 ppm and preferablybetween 0 and 100 ppm, with respect to the monomers of the mixture,

The impregnation process according to the invention for impregnating afibrous substrate comprises a step of impregnating the fibrous substratewith a liquid (meth)acrylic syrup.

A simple (meth)acrylic monomer or a (meth)acrylic monomer mixture asliquid (meth)acrylic syrup is too liquid for the impregnation process ofthe present invention, especially for the correct and complete wettingand impregnation of the fibrous substrate. Therefore the viscosity hasto be adapted by increasing it.

With regard to the liquid (meth) acrylic syrup according to theinvention that impregnates the fibrous substrate, it comprises a(meth)acrylic monomer or a mixture of a (meth)acrylic monomers, a(meth)acrylic polymer and at least one initiator or initiating systemfor starting the polymerization of the (meth) acrylic monomer.

According to the invention the viscosity is increased by using(meth)acrylic monomer or a mixture of a (meth)acrylic monomers withdissolved (meth)acrylic polymer or (meth)acrylic polymers. This solutionis commonly referred to as “syrup” or “prepolymer”.

Advantageously the liquid (meth) acrylic syrup contains no additionallyvoluntary added solvent.

The (meth)acrylic polymer is completely soluble in the (meth)acrylicmonomer.

This (meth)acrylic polymer is PMMA, meaning the homo- or copolymer ofmethyl methacrylate (MMA) or a mixture thereof as defined before.

This (meth)acrylic monomer is the same as defined before.

The (meth)acrylic monomer or the (meth)acrylic monomers in the liquid(meth) acrylic syrup present at least 40% by weight, preferably 50% byweight, advantageously 60% by weight and more advantageously 65% byweight of total liquid (meth) acrylic syrup in view of (meth)acrylicmonomer and (meth)acrylic polymer.

The (meth)acrylic monomer or the (meth)acrylic monomers in the liquid(meth) acrylic syrup present at most 90% by weight, preferably at most85% by weight, advantageously at most 82% by weight and moreadvantageously at most 80% by weight of total liquid syrup in view of(meth)acrylic monomer and (meth)acrylic polymer.

The (meth)acrylic polymer or polymers in the liquid (meth) acrylic syruppresent at least 10% by weight, preferable at least 15%, advantageouslyat least 18% and more advantageously at least 20% by weight of totalliquid (meth) acrylic syrup in view of (meth)acrylic monomer and(meth)acrylic polymer.

The (meth)acrylic polymer or polymers in the liquid (meth) acrylic syruppresent at most 60% by weight, preferable at most 50%, advantageously atmost 40% and more advantageously at most 35% by weight of total liquid(meth) acrylic syrup.

The (meth)acrylic monomer or the (meth)acrylic monomers in the liquid(meth) acrylic syrup presents from 40% to 90% by weight, preferably from50% to 90% by weight, advantageously from 55% to 85% by weight and moreadvantageously from 60% to 80% by weight of total liquid syrup in viewof (meth)acrylic monomer and (meth)acrylic polymer.

Accordingly (meth)acrylic polymer or polymers in the liquid (meth)acrylic syrup presents from 60% to 10% by weight, preferably from 50% to10% by weight, advantageously from 15% to 45% by weight and moreadvantageously from 20% to 40% by weight of total liquid syrup in viewof (meth)acrylic monomer and (meth)acrylic polymer.

The dynamic viscosity of the liquid (meth) acrylic syrup is in a rangefrom 10 mPa*s to 10000 mPa*s, preferably from 50 mPa*s to 5000 mPa*s andadvantageously from 100 mPa*s to 1000 mPa*s. The viscosity of the syrupcan be easily measured with a Rheometer or viscosimeter. The dynamicviscosity is measured at 25° C. The liquid (meth) acrylic syrup has aNewtonian behaviour, meaning no shear thinning, so that the dynamicviscosity is independent of the shearing in a rheometer or the speed ofthe mobile in a viscosimeter.

If the viscosity of the liquid (meth) acrylic syrup at a giventemperature is too high for the impregnation process and for the correctimpregnation, it is possible to heat the syrup in order to have a moreliquid syrup within the before mentioned dynamic viscosity interval atthe respective temperature during which the impregnation takes place forthe sufficient wetting and correct and complete impregnation of thefibrous substrate.

The liquid syrup according to the present invention does not contain anyadditional solvent voluntary added.

The liquid (meth) acrylic syrup may comprise also other additives andfillers. A filler in the scope of the present invention is notconsidered as an additive.

All the additives and fillers can be added to the liquid (meth) acrylicsyrup before the impregnation.

As additives one can mention organic additives as impact modifiers orblock copolymers, thermal stabilizers, UV stabilizers, lubricants andmixtures thereof.

The impact modifier is in the form of fine particles having anelastomeric core and at least one thermoplastic shell, the size of theparticles being in general less than 1 μm and advantageously between 50and 300 nm. The impact modifier is prepared by emulsion polymerization.The impact modifier content in the liquid (meth) acrylic syrup is from 0to 50 wt %, preferably from 0 to 25 wt %, and advantageously from 0 to20% by weight.

As fillers one can mention carbon nanotubes or mineral charges includingmineral nano charges (TiO2, silica).

The filler content in the liquid (meth) acrylic syrup is from 0 to 20 wt%.

An additional aspect according to the present invention is theimpregnation process, for impregnating a fibrous substrate, wherein saidfibrous substrate is made of long fibres and said process comprises astep of impregnating said fibrous substrate with a liquid (meth) acrylicsyrup comprising:

-   -   a) from 10 wt % to 59.99 wt % (meth)acrylic polymer,    -   b) from 40 wt % to 89.99 wt %(meth)acrylic monomer,    -   c) from 0.01 wt % to 5 wt % one initiator or initiating system        for starting the polymerization of the (meth) acrylic monomer,    -   d) from 0 wt % to 1 wt % activator,    -   e) from 0 wt % to 20 wt % filler,    -   f) from 0 wt % to 20 wt % additives.

Another additional aspect according to the present invention is theimpregnation liquid (meth) acrylic syrup for implementing theimpregnation process according to any of the preceding claims, saidliquid (meth) acrylic syrup comprises

-   -   a) a (meth)acrylic polymer,    -   b) a (meth)acrylic monomer,    -   c) at least one initiator or initiating system for starting the        polymerization of the (meth) acrylic monomer,        said liquid (meth)acrylic syrup has a dynamic viscosity of a        value in the range from 10 mPa*s to 10000 mPa*s, preferably from        50 mPa*s to 5000 mPa*s and advantageously from 100 mPa*s to 1000        mPa*s.

Still another additional aspect according to the present invention is animpregnation liquid (meth) acrylic syrup comprising:

-   -   from 10 wt % to 59.99 wt % (meth)acrylic polymer,    -   from 40 wt % to 89.99 wt %(meth)acrylic monomer,    -   from 0.01 wt % to 5 wt % one initiator or initiating system for        starting the polymerization of the (meth) acrylic monomer,    -   from 0 wt % to 1 wt % activator,    -   from 0 wt % to 20 wt %    -   from 0 wt to 20 wt % in additives.

Still another aspect of the present invention is a manufacturing processfor manufacturing mechanical or structured parts or articles comprisingfollowing steps:

-   -   a) impregnating a fibrous substrate with a liquid (meth) acrylic        syrup,    -   b) polymerising the liquid (meth) acrylic syrup impregnating        said fibrous substrate.

Preferably the impregnation of the fibrous substrate in step a) is madein a closed mold.

Advantageously the step a) and step b) are made in the same closedmould.

The mold is opaque towards visible and ultraviolet radiation at least onone side

A closed mold will amongst other things avoid and reduce the evaporationof the monomer and protect the environment.

Using the same closed mold will avoid the transfer of the material afterimpregnation and polymerizing in a closed mold will guarantee a gooddistribution of the heat, having a satisfying yield of polymerizationand eventually evaporation of the monomer(s).

No metals are present in manufactured mechanical or structured parts orarticles such as tin are present coming from accelerators added for thepolymerization step.

The manufactured mechanical or structured parts or articles do notcontain any additional solvent voluntary added, since the syrup did notcontain any additional solvent for the impregnation step.

With regard to the manufactured mechanical or structured parts orarticles of the present invention, it comprises at least 20% by weightof fibrous substrate, preferable at least 40% by weight of fibrousmaterial advantageously at least 50% by weight of fibrous material andadvantageously at least 55% by weight of fibrous material based on thetotal composition.

The manufactured mechanical or structured parts or articles of thepresent invention, it comprises at most 99% by weight of fibrousmaterial, preferable at most 95% by weight of fibrous materialadvantageously at most 90% by weight of fibrous material andadvantageously at most 80% by weight of fibrous material based on thetotal composition.

Due to the manufacturing process for manufacturing mechanical orstructured parts or articles according to the invention a complete,correct and homogenous wetting of the fibrous substrate duringimpregnation takes place. There are no defects of fiber wetting duringimpregnation for example by bubbles and voids that decrease themechanical performance of the manufacturing mechanical or structuredparts or articles.

The manufactured mechanical or structured parts or articles according tothe invention do not comprise essentially any pores. By pore is meant aspherical void with a diameter of at least 1 μm or larger or anelongated ellipsoidal void in form of an oblate with a smallestprincipal axe of at least 0.5 μm or larger. By “comprising essentiallyno pores” is meant that the pores represent less then 1 vol %,preferably less then 0.5 vol % and more preferably less then 0.2 vol %of the total volume of the manufactured mechanical or structured partsor articles.

With regard to manufacturing process for manufacturing mechanical orstructured parts or articles comprising the polymeric compositematerial, several methods could be used in order to preparethree-dimensional mechanical or structured parts. One can mentioninfusion, vacuum bag moulding, pressure bag molding, autoclave molding,resin transfer moulding (RTM), reaction injection molding (RIM)reinforced reaction injection molding (R-RIM) and variants thereof,press molding or compression molding.

The preferred manufacturing process for manufacturing mechanical orstructured parts or articles comprising the composite materials areprocesses were the liquid (meth) acrylic syrup transferred to thefibrous substrate by impregnating the fibrous substrate in a mold morepreferably in a closed mold.

Advantageously the impregnation step of the fibrous material is made ina closed mold.

Most advantageously the manufacturing process for manufacturingmechanical or structured parts or articles comprising the polymericcomposite material is chosen from resin transfer molding or infusion.

All processes comprise the step of impregnating the fibrous substratewith the liquid (meth) acrylic syrup before the polymerization step in amold.

The step of polymerising of the liquid (meth) acrylic syrup impregnatingsaid fibrous substrate takes place after the impregnation step in thesame mold.

Resin transfer molding is a method using a two sided mold set whichforms both surfaces of composite material. The lower side is a rigidmould. The upper side can be a rigid or flexible mould. Flexible mouldscan be made from composite materials, silicone or extruded polymer filmssuch as nylon. The two sides fit together to produce a mould cavity. Thedistinguishing feature of resin transfer moulding is that the fibroussubstrate is placed into this cavity and the mould set is closed priorto the introduction of the liquid (meth) acrylic syrup. Resin transfermoulding includes numerous varieties which differ in the mechanics ofhow the liquid (meth) acrylic syrup is introduced to the fibroussubstrate in the mould cavity. These variations include everything fromvacuum infusion to vacuum assisted resin transfer moulding (VAR™). Thisprocess can be performed at either ambient or elevated temperature.Ambient temperature means between 10° C. and 50° C. Elevated temperaturemeans up to 200° C. Preferably elevated temperature is from 50° C. up to160° C.

With the infusion method the liquid (meth) acrylic syrup does have tohave the adapted viscosity towards this preparation method of thepolymeric composite material. The liquid (meth) acrylic syrup is aspiredinto the fibrous substrate present in a special mold by application of aslight vacuum. The fibrous substrate is infused and completelyimpregnated by the liquid (meth) acrylic syrup.

One advantage of this method is the high amount of fibrous material inthe composite.

With regard to the use of manufactured mechanical or structured parts orarticles, one can mention automotive applications, nauticalapplications, railroad applications, sport, aeronautic and aerospaceapplications, photovoltaic applications, computer related applications,telecommunication applications and wind energy applications.

Particularly the three-dimensional mechanical or structured part is aautomobile part, boat part, train part, sport article, plane orhelicopter part, space ship or rocket part, photovoltaic module part,wind turbine part, furniture part, construction or building part,telephone or cell phone part, computer or television part, printer andphotocopy part.

With regard to the recycling of the structured part, comprising thethermoplastic composite material it can be made by grinding ordepolymerization of the thermoplastic polymer.

Grinding is made mechanically in order to obtain smaller parts ofpieces. As the structured part compromises thermoplastic polymer, thispolymer can be heated, and the pieces again transformed in a certainlimit in order to obtain a recycled object.

Preferably the structured part comprising the thermoplastic composite isheated for making a pyrolysis or thermal decomposition of the PMMA andrecovering the methyl methacrylate as monomer.

Advantageously at least 50 wt % of the MMA present in the polymer arerecovered by thermal decomposition.

The structured part is heated at a temperature of at least 200° C. andno more than 400° C.

So, a final subject of the present invention relates to the use of theimpregnation process or of the manufacturing process according to theinvention, particularly when the said methacrylic polymer is anhomopolymer or/and a copolymer of methyl methacrylate, in themanufacture of mechanical and/or structural parts which are recyclableby thermal depolymerisation (by means of pyrolysis), preferably with atleast 50% of the monomers, particularly of methyl methacrylate(MMA)recovered.

EXAMPLES Example 1

A syrup is prepared by dissolving 25 parts by weight of the PMMA (BS520copolymer of MMA comprising ethyl acrylate as a comonomer) in 75 partsby weight of methyl methacrylate, which is stabilized with MEHQ(hydroquinone monomethyl ether). To the 100 parts by weight of the syrupare added 2 parts by weight of benzoyl peroxide (BPO—Luperox A75 fromARKEMA) and 0.2 parts by weight of DMPT (N,N-dimethyl-p-toluidine fromSigma-Aldrich). The syrup has a dynamic viscosity of 520 mPa*s at 25° C.The syrup is injected in a closed mould comprising a glass fabric asfibrous substrate and polymerized at 25° C. during 80 minutes.

A structural part in form of a sheet is obtained from the mould.

The sheet has a good adherence of the thermoplastic polymer to thefibrous substrate.

The sheet possesses also satisfying mechanical properties.

After utilisation the structural part in form of a sheet can be recycledby heating and depolymerisation.

What is claimed is:
 1. An impregnation liquid (meth) acrylic syrup forimplementing an impregnation process of a fibrous substrate, whereinsaid fibrous substrate is made of long fibres having an aspect ratio ofat least 1000, said liquid (meth) acrylic syrup comprises: a) a(meth)acrylic polymer comprising at least 90 percent by weight of methylmethacrylate monomer units and having a weight average molecular weightlarger than 50,000 g/mol, b) a (meth) acrylic monomer comprising aninhibitor, wherein said (meth)acrylic monomer is two or more selectedfrom the group consisting of acrylic acid, methacrylic acid, alkylacrylic monomers wherein said alkyl has 1 to 22 carbons, either linear,branched or cyclic; alkyl methacrylic monomers wherein said alkyl has 1to 22 carbons, either linear, branched or cyclic; methyl methacrylate,ethyl methacrylate, methyl acrylate, ethyl acrylate, n-butyl acrylate,iso-butyl acrylate, n-butyl methacrylate, iso-butyl methacrylate,cyclohexyl acrylate, cyclohexyl methacrylate, isobornyl acrylate,isobornyl methacrylate and mixtures thereof c) at least one initiator orinitiating system for starting the polymerization of the (meth) acrylicmonomer, and d) from 300 ppm to 4000 ppm by weight of an activator,based on the weight of the (meth) acrylic monomer said liquid(meth)acrylic syrup has a dynamic viscosity of a value in the range from50 mPa*s to 1000 mPa*s, and wherein said syrup contains no metal basedcatalysts.
 2. The impregnation liquid (meth) acrylic syrup according toclaim 1, wherein said syrup comprises: a) from 10 weight percent to59.99 weight percent (meth)acrylic polymer, based on the sum of the(meth)acrylic monomer plus (meth)acrylic polymer, b) from 40 weightpercent to 89.99 weight percent (meth)acrylic monomer, c) from 0.01weight percent to 5 weight percent one initiator or initiating systemfor starting the polymerization of the (meth) acrylic monomer, based onthe weight of the (meth)acrylic monomer, d) from 300 ppm to 4000 ppm byweight of an activator, based on the weight of the (meth) acrylicmonomer e) from 0 weight percent to 20 weight percent fillers, based onthe weight of the liquid (meth)acrylic syrup, f) from 0 weight percentto 20 weight percent additives based on the weight of the liquid(meth)acrylic syrup.
 3. The impregnation liquid (meth) acrylic syrupaccording to claim 1, wherein the (meth)acrylic polymer is a homopolymeror copolymer of methyl methacrylate (MMA) units or a mixture thereof. 4.The impregnation liquid (meth) acrylic syrup according to claim 1,wherein the (meth)acrylic polymer comprises at least 95 percent byweight of methyl methacrylate (MMA) units.
 5. The impregnation liquid(meth) acrylic syrup according to claim 1, wherein the (meth)acrylicpolymer comprises from 90 percent to 99.7 percent by weight of methylmethacrylate units, and from 0.3 to 10 percent by weight of at least onemonomer unit derived from at least one ethylenic unsaturation that cancopolymerize with methyl methacrylate.
 6. The impregnation liquid (meth)acrylic syrup according to claim 1, wherein the (meth)acrylic polymerfurther comprises comonomer units, wherein said comonomer units are analkyl acrylate having an alkyl group from 1 to 12 carbon atoms.
 7. Theimpregnation liquid (meth) acrylic syrup according to claim 6, whereinsaid comonomer units are chosen from methyl acrylate, ethyl acrylate,and a mixture thereof.
 8. The impregnation liquid (meth) acrylic syrupaccording to claim 1, wherein the (meth)acrylic polymer has polymerweight average molecular weight larger than 100,000 g/mol.
 9. Theimpregnation liquid (meth) acrylic syrup according to claim 1, whereinat least 50 weight percent of the (meth)acrylic monomer is methylmethacrylate.
 10. The impregnation liquid (meth) acrylic syrup accordingto claim 1, wherein the initiator or initiating system for starting thepolymerization of the (meth) acrylic monomer generates radicals.
 11. Theimpregnation liquid (meth) acrylic syrup according to claim 10, whereinthe initiator or initiating system for starting the polymerization ofthe (meth) acrylic monomer is selected from the group consisting ofdiacyl peroxides, peroxy esters, dialkyl peroxides, peroxyacetals, azocompounds, isopropyl carbonate, benzoyl peroxide, lauroyl peroxide,caproyl peroxide, dicumyl peroxide, tert-butyl perbenzoate, tert-butylper(2-ethylhexanoate), cumyl hydroperoxide,1,1-di(tert-butylperoxy)-3,3,5-trimethylcyclohexane, tert-butylperoxyisobutyrate, tert-butyl peracetate, tert-butyl perpivalate, amylperpivalate, tert-butyl peroctoate, azobisisobutyronitrile (AIBN),azobisisobutyramide, 2,2′-azobis(2,4-dimethylvaleronitrile) or4,4′-azobis(4-cyanopentanoic) and mixtures thereof.
 12. The impregnationliquid (meth) acrylic syrup according to claim 11, wherein the initiatoror initiating system for starting the polymerization of the (meth)acrylic monomer is chosen from peroxides having 2 to 20 carbon atoms.13. The impregnation liquid (meth) acrylic syrup according to claim 11,wherein the amount of the initiator or initiating system for startingthe polymerization of the (meth) acrylic monomer is from 100 to 50000ppm by weight, based on the (meth)acrylic monomer.
 14. The impregnationliquid (meth) acrylic syrup according to claim 2, wherein the liquid(meth) acrylic syrup comprises 300 to 4,000 ppm by weight based on theweight of (meth)acrylic monomer, of an activator, said activator beingselected from the group consisting of tertiary amines,N,N-dimethyl-p-toluidine (DMPT), N,N-dihydroxyethyl-p-toluidine (DHEPT),and mixtures thereof.
 15. The impregnation liquid (meth) acrylic syrupaccording to claim 1, wherein the (meth)acrylic polymer in the liquid(meth) acrylic syrup is present at from 15 weight percent to 50 weightpercent, based on the total liquid (meth) acrylic syrup.
 16. Theimpregnation liquid (meth) acrylic syrup according to claim 2, whereinsaid additive is selected from the group consisting of impact modifiers,block copolymers, thermal stabilizers, UV stabilizers, flame retardants,lubricants and mixtures thereof.
 17. A manufacturing process formanufacturing mechanical or structured parts or articles comprisingfollowing steps: a) impregnating a fibrous substrate with theimpregnation liquid (meth) acrylic syrup according claim 1, b)polymerizing the liquid (meth) acrylic syrup impregnating said fibroussubstrate.
 18. The process according to claim 17, wherein said fibroussubstrate consists of fibers have an aspect ratio of at least
 1000. 19.The process according to claim 17, wherein the fibrous substrate is inform of fibrous mats, non-woven reinforcements, woven roving or bundlesof fibers.
 20. The process according to claim 17, wherein theimpregnation of the fibrous substrate in step a) is made in a closedmold.
 21. The process according to claim 17, wherein step a) and step b)occur in the same closed mold.
 22. The process according to claim 17,wherein the process is chosen from resin transfer molding and infusion.23. The process according to claim 17, wherein the temperature of thepolymerization is step b) is below 40° C.
 24. A three-dimensionalmechanical or structured parts obtained by the manufacturing processaccording to claim
 17. 25. The three-dimensional mechanical orstructured parts according to claim 24, wherein said part is selectedfrom the group consisting of an automobile part, boat part, train part,sport article, plane or helicopter part, space ship or rocket part,photovoltaic module part, wind turbine part, furniture part,construction or building part, telephone or cell phone part, computer ortelevision part, printer part, and photocopy part.
 26. The impregnationliquid (meth) acrylic syrup according to claim 1, wherein the liquid(meth) acrylic syrup contains from 20 wt % to 40 wt % of the(meth)acrylic polymer, in view of the total weight of the (meth)acrylicpolymer and (meth)acrylic monomer, and from 60 wt % to 80 wt % of the(meth)acrylic monomer in view of the total weight of the (meth)acrylicpolymer and (meth)acrylic monomer.
 27. An impregnation liquid (meth)acrylic syrup for implementing an impregnation process of a fibroussubstrate, wherein said fibrous substrate is made of long fibres havingan aspect ratio of at least 1000, said liquid (meth) acrylic syrupcomprising: a) a (meth)acrylic polymer comprising at least 90 percent byweight of methyl methacrylate monomer units and having a weight averagemolecular weight larger than 50,000 g/mol, and b) two or more(meth)acrylic monomers selected from the group consisting of acrylicacid, methacrylic acid, alkyl acrylic monomers wherein said alkyl has 1to 22 carbons, either linear, branched or cyclic; alkyl methacrylicmonomers wherein said alkyl has 1 to 22 carbons, either linear, branchedor cyclic; methyl methacrylate, ethyl methacrylate, methyl acrylate,ethyl acrylate, n-butyl acrylate, iso-butyl acrylate, n-butylmethacrylate, iso-butyl methacrylate, cyclohexyl acrylate, cyclohexylmethacrylate, isobornyl acrylate, isobornyl methacrylate and mixturesthereof, and an inhibitor; the liquid (meth) acrylic syrup furtherincluding: c) at least one initiator or initiating system for startingthe polymerization of the (meth) acrylic monomer, and d) from 300 ppm to4000 ppm by weight of an activator, based on the weight of the (meth)acrylic monomer, said liquid (meth)acrylic syrup has a dynamic viscosityof a value in the range from 10 mPa*s to 1000 mPa*s, and wherein saidsyrup contains no metal based catalysts.